Cellulosic composition of matter containing chloro-cyclohexane



Oct. 6, 1931. 1,826,689

CELL-ULOSIC COMPOSITION of MATTER CONTAINING CHLOROr-CYCLOHEXANE s. .1. CARROLL Filed Aug. 50. 1929 0 0 w m 9 w m D B INA O 0 w M M 0 .5 4 3 2 m M PLASTICIZER.

Patented a. 6, 1931 lam ' STEWART. J.- CARROLL, or stamens, new YORK, ASSIGNOR To-EAsTMAN KODAK Germany, or ROCHESTER, ew YORK, A CORPORATION- OF NEw'YoRK oELLuLosIc .colurosirrou or mwmaeemimme cnnoao-cycronnxanr.

Application filediAug'ust 30,1929} Serial No. 389,452. i

This invention relates: to compositions of matter in which cellulose derivatives, such as cellulose acetate," cell'ulose nitrate I or cellulose ether, are combined or mixed with othersub- 5' stances, such as'a compatibleplasticizer, and

a common 'solventfor' both, "with or without other useful addition-agents, so that the resulting product: will have properties such as make the composition hig-hly adv'anta- IOBg'eous for use in the plastic and *analogous arts-such, for instance, as themanufacture of Wrapping sheets,photographic film, artificial silk, varnishes or lacquers, and the like. One object of this invention is to produce a composition of matter-which may be made into permanently transparent, strong and flexible sheets or films of desired thinness which are substantially waterproofllareuns affected byordinary photographic fluidsand possess the desiredproperties ofasupport-for sensitive: photographic coatings? ;Another object of my invention is to' produce'a-composition which is capable of easy and convenient manipulation in the plastic and analagou's 2! arts, such as in the 'manu'facturefof sheets,

films, artificial silk filaments, varnishes,fla cquers and the like; and to'produceacomposi-' tion which will not" injure, or be injured by, the substances or surfaces with which it is as- 9 90 sociated during manufacture, storageoruse; Other and further'objects will hereinafter b ecome apparent tothoseskilledfinthe which this inventid s -t pi r 1 A While cellulose acetates, nitratesand ethe' art to 38 have been known forfdecades ithas 'also been kn own that to utilize'them in the yarious plas-' tic arts it isn'ecess'ary to m x 'therewith such-v plasti cizing or conditioning'jagentsas camv phor, 'castor oil, triphenyl phosphate, monochlornaphthaleneorthe' like. Certain of these aridotheradditiOn agents are also added I for the purpose ofr'ed-ucing the inflammabil ity of the product Plastic inducing agents such as the higher alcohols and their esters, 5 are sometimesalso added. Similarly addition compounds of various kinds I have been em ployed to increase flexibility,transparency, V toughness andother' properties which will'en-= hance' the value of the resulting--product Addition products'for the'same or similar P 1rposes arealso added'vto cellulose-acetate nitrates and ethersto prepare them for use in'the other plastic arts, such as in the manu-, Y

facture "of'lacquers, varnishes, artificial silk filaments, moulded compounds .and'thelike; In I Wlllle the plasticizers or other: addition economical plasticizers .or other addition agents a matterof considerable importance to'theart 3 f I havediscoveredthat valuable properties "may be induced in and/or contributed to compos tions COIltZLlIllIlgCGllUlQSG derivatives,

such as cellulose acetate, by adding thereto the plasticizing compound 'chloro-cyclohexane in the presence of a solvent, such as acetone'which willdissolve both the cellulose derivativeandplasticizer. This plasticizer "is a liquid at ordinary atmospheric 'tempera- W has the r c ral formulaiof 1 It is-compatible with cellulose derivatives'aiid particularly compatible with cellulose acetate in the percentages hereinafter given. It is not anexpensive com'pound andznotparticularly diflicult to produce, or obtain-upon the open market. The particularly usefulproperti'es which itv induces in or contribut'estoa cellulosic composition containing it are here inafter enumerated.

containing "from 36%t0 42%acetyl radical, .100 I approximately, is dissolved with stirring at atmospherictemperature in 300 to 500 parts, 7

v v Inorder that those skilled in this art'may preferably 400 parts, by weight, of acetone. To this solution may be added from 10 to 30 parts by weight, of chloro-cyclohexane, it be ing found preferable to employ approximately 30 parts thereof. Within the limits stated, the amount of plasticizer may be decreased or increased, depending upon whether it is desired to decrease or increase, respectively, the properties which this plasticizer contributes to the finished product. The amount of solvent employed may also be decreased or increased, depending upon whether it is de sired to have a. more or less freely flowing composition. respectively.

A composition of matter prepared as above described may be deposited upon any suitable film forming surface to form a film or sheet, as is well known to those skilled in the art. A film so produced has permanently brilliant transparency and low infiammability, burning no more readily than ordinary newsprint. Such film is tough and flexible as shown by the fact that it will withstand many folds upon a modified Schopper fold-tester (commonly used for such purposes) without breaking and that even after being subjected for 191 days to air maintained at a temperature of C. the film still maintains flexibility, demonstrating that the film will withstand ordinary usage satisfactorily for many years, whereas a film formed from a mere solution of cellulose acetate in acetone or other similar solvent is brittle and fragile after being subjected to the same treatment for as little as thirty days or even a lesser time. The sum total of the above advantageous properties of a product produced from my new composition is considerably in excess of that of products produced with what havepreviously been regarded as the better plasticizers.

Other similar solvents instead of acetone) which are compatible with the cellulose acetate and my new plasticizer may also occur to those skilled in this art. In like manner this plasticizer may be compounded with other single organic esters of cellulose, such as cellulose propionate, butyrate and the like, or with mixed organic and/or inorganic esters, such as cellulose aceto-stearate, acetomalate, or cellulose nitro-acetate, or with the cellulose ethers, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer being employed.

. The accompanying drawing, forming a partof this application. clearly illustrates the particular advantages of employing my novel plasticizer in the plastic arts. In this drawing there are plotted lines or curves graphically depicting the properties of film produced from a composition containing cellu lose acetate and this plasticizer. On the horizonta-l axis is indicated the various percentages of my plasticizer that may be employed with the cellulosic derivative, this percentage being given in parts added to the cellulose derivative rather than parts of the composition for instance, 30 parts plasticizer added to 100 parts cellulose acetate is denoted as 30% plasticiz'er added. On the vertical axis at (a), on the left, is indicated in percentage over the check sample the initial flexibility of a film which has been formed as described from my novel composition and which has been subjected to air at 50 C. for 24 hours to free it of solvent; the rate of combustion of that film is also indicated by this same column (a) at (b) on the right is indicated the length of time in days that the film will maintain flexibility when subjected to air kept at a temperature of 65 C. The curve (A) depicts initial flexibility of the film, the curve (B) depicts the ability of the film to main.- tain flexibility and the curve (C) depicts the rate of combustion of the film-all with various percentages of my novel plasticizer and all as compared to the respective properties of a film produced from a solution of cellulose acetate in acetone and a hypothetical inert materialsubstituted for the plasticizer as denoted bycurve (D) indicating unity of so 100% and 30 days for (a) and It will thus be noted that my novel plasticizer has the faculty of giving, to a product produced therefrom, good initial flexibility and a low combustion rate, and that the product main- -95 tains its flexibility quite well. The preferred percentage of my plasticizer which it is desirable to employ to contribute any particular property to the final product will be obvious from an inspection of this drawing; the best 0 percentage to employ will depend upon which property it is desired to feature most in the final product.

Inasmuch as my above described composition of matter is quite useful in the production of films and sheets it will be apparent that my new plasticizer may also be employed with advantage in the other branches of the plastic art. For instance, my above described composition of matter may be em- 1 ployed in the manufacture of artificial silk by i the dry spinning method. With the proper coagulating bath it may also be employed for wet spinning. It may be desired to employ a composition of different viscosity or evaporation characteristics but this is a mere matter of changing the solvent proportion or adding evaporation retardants such as triacetin or other high or intermediate boiling constituents, as has been well known in the art for more than a decade. My novel plasticizer may'also be employed with advantage in connection with a number of the known lacquer and varnish formulae with which it may be found to be compatible. In such cases the plasticizer is usually first put into solution with the cellulose derivative solution and if non-solvents are added for the purpose of cheapening the composition they are added only to such an extent as will not precipitate 1'30 the deritative from solution; Other uses 7 Within the scope'of my invention will also 7 suggest themselves to those skilled in the art.

What I claim as my invention, an d desire, to be secured by Letters Patent of the United States, is:

r 1. A compositionofxmatter comprising a cellulose derivative and chloro-cyclohexane. 1

- 2. Acomposition of matter comprising cellulose acetate and chloro-cyclohexane.

3. A composition of matter comprising 100 parts cellulose acetate and from about 10 to I 30 parts, by Weight, of chloro-cyclohexane.

4:. A composition of mattercomprising 100' I parts of cellulose acetate and approximately 30 g arts, by Weight, of chloro-cyclohexane'.

gned at Rochester,'l TeW- York this 27th 7 day ofAugust, 1929. r

; STEWART J. CARROLL. 

